CN102481503A - Ceramic honeycomb structure and method for manufacturing same - Google Patents

Ceramic honeycomb structure and method for manufacturing same Download PDF

Info

Publication number
CN102481503A
CN102481503A CN2010800376698A CN201080037669A CN102481503A CN 102481503 A CN102481503 A CN 102481503A CN 2010800376698 A CN2010800376698 A CN 2010800376698A CN 201080037669 A CN201080037669 A CN 201080037669A CN 102481503 A CN102481503 A CN 102481503A
Authority
CN
China
Prior art keywords
pore
particle
ceramic honeycomb
diameter
honeycomb structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2010800376698A
Other languages
Chinese (zh)
Other versions
CN102481503B (en
Inventor
冈崎俊二
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Proterial Ltd
Original Assignee
Hitachi Metals Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Metals Ltd filed Critical Hitachi Metals Ltd
Publication of CN102481503A publication Critical patent/CN102481503A/en
Application granted granted Critical
Publication of CN102481503B publication Critical patent/CN102481503B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2068—Other inorganic materials, e.g. ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0001—Making filtering elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/2429—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material of the honeycomb walls or cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/24491—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/24492—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/24494—Thermal expansion coefficient, heat capacity or thermal conductivity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2455—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the whole honeycomb or segments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2474—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the walls along the length of the honeycomb
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2482—Thickness, height, width, length or diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418—Honeycomb filters
    • B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2484—Cell density, area or aspect ratio
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C04B35/195—Alkaline earth aluminosilicates, e.g. cordierite or anorthite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006—Honeycomb structures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006—Honeycomb structures
    • C04B38/0009—Honeycomb structures characterised by features relating to the cell walls, e.g. wall thickness or distribution of pores in the walls
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/063—Preparing or treating the raw materials individually or as batches
    • C04B38/0635—Compounding ingredients
    • C04B38/0645—Burnable, meltable, sublimable materials
    • C04B38/067—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/063—Preparing or treating the raw materials individually or as batches
    • C04B38/0635—Compounding ingredients
    • C04B38/0645—Burnable, meltable, sublimable materials
    • C04B38/068—Carbonaceous materials, e.g. coal, carbon, graphite, hydrocarbons
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/1208—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/1216—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/125—Size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/1258—Permeability
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3445—Magnesium silicates, e.g. forsterite
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/06—Ceramic, e.g. monoliths
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24149—Honeycomb-like

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Geometry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Filtering Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Nanotechnology (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)

Abstract

A ceramic honeycomb structure having a plurality of flow paths which are partitioned by porous bulkheads, wherein the porosity of the bulkheads is 40-60%, the opening area ratio (the total opening area of pores which are open per unit area of the surfaces of the bulkheads) of the pores which are open on the surfaces of the bulkheads is 15% or more, the median opening diameter based on the area of the pores which are open is 10 [mu]m or more but less than 40 [mu]m when the opening diameter of the pores which are open on the surfaces of the bulkheads is expressed by circle-equivalent diameter (the diameter of a circle having an area equivalent to the opening area of the pores), the density of the pores in which the circle-equivalent diameter is 10 [mu]m or more but less than 40 [mu]m is 350 pieces/mm2 or more, and the average value of the degrees of circularity of the pores in which the circle-equivalent diameter is 10 [mu]m or more but less than 40 [mu]m is 1-2.

Description

Ceramic honeycomb structure and manufacturing approach thereof
Technical field
The present invention relates to the ceramic honeycomb structure that in the ceramic honeycomb filter of the contained particulate of the waste gas that is used for removing diesel engine, uses.
Background technology
In the waste gas of Diesel engine; Contain with coal ash that constitutes by carbonaceous and the SOF composition that constitutes by higher boiling point hydrocarbon compound composition (Soluble Organic Fraction: the solubility organic principle) be PM (the Particulate Matter: particle-like substance) of principal component; If it is discharged in the atmosphere, then possibly bring harmful effect to human body and environment.Therefore, be used to catch the ceramic honeycomb filter of collecting PM installing of the blast pipe of Diesel engine midway all the time.
One example of the ceramic honeycomb filter of the PM in seizure collection, the purifying exhaust air is shown in Fig. 1 and Fig. 2.Ceramic honeycomb filter 10 comprises: the ceramic honeycomb structure that is made up of porous matter next door 2 that forms a plurality of outflow sides sealing stream 3 and inflow side sealing stream 4 and periphery wall 1, waste gas inflow side end face 8 and waste gas outflow side end face 9 that the outflow side is sealed stream 3 and inflow side sealing stream 4 alternately are sealed to latticed upstream side seal 6a of portion and the 6c of downstream side seal portion.The said periphery wall 1 of ceramic honeycomb filter is controlled and in use can not be moved through the member (not shown) of controlling that is formed by the pad of wire netting or pottery system etc., and in the metal system of the being configured in accommodating container (not shown).
In ceramic honeycomb filter 10, carry out the purification of waste gas in such a way.Waste gas such outflow side sealing stream 3 from end face 8 openings in the waste gas inflow side shown in the dotted arrow of Fig. 2 flows into.Then, when waste gas when the next door 2, particularly for through the time by surface that is present in next door 2 and intercommunicating pore that the inner pore that communicates with each other forms, the collection that is captured of the PM in the waste gas.Sealing stream 4 flows out and is discharged into the atmosphere waste gas after the purification from the inflow side of end face 9 openings in the waste gas outflow side.
When PM continues to be caught when collecting by next door 2, the surface and the inner intercommunicating pore in next door 2 are stopped up by PM, thereby the pressure loss of waste gas during through ceramic honeycomb filter increases to some extent.Therefore, need arrive setting in the pressure loss and before ceramic honeycomb filter regeneration removed and made in the PM burning.
Ceramic honeycomb filter need satisfy following requirement, that is, the seizure collection rate of particulate is high, and the pressure loss is low.Yet,, satisfy these two simultaneously through the control porosity, pore volume, the size etc. that is present in the pore on surface, next door and require to realize optimization so study all the time because these characteristics are opposite relations.
The special table of Japan has been put down in writing following ceramic filter 2005-530616 number; Promptly; It is made up of the cordierite honeycomb tectosome that the end is inaccessible; Distribute the value d50/ (d50+d90) obtain less than 0.70 according to fine pore, transmitance factor S f was less than 1.55 when the coal ash through formula [d50/ (d50+d90)]/[% porosity rate/100] definition adhered to, and thermal coefficient of expansion (25～800 ℃) is 17 * 10 -7/ ℃ below, the diesel exhaust gas particulate caught makes its burning, through having this pore structure (fine pore distributes and the pore connectivity), even under the state that the carbon ash adheres to, also can keep the less pressure loss.
Put down in writing following porous matter amplifier case for TOHKEMY 2002-219319 number; That is, it is that the material of principal crystalline phase constitutes by the cordierite control so that pore is distributed, and said pore is distributed as: fine pore is below 15% of whole pore volume less than the pore volume of 10 μ m; The pore volume of fine pore 10～50 μ m is more than 75% of whole pore volume; The pore volume that fine pore surpasses 50 μ m is below 10% of whole pore volume, because having described pore, this porous matter amplifier case distributes, so; Seizure collection efficiency to PM etc. is high, and can prevent to stop up because of pore the increase of the pressure loss that causes.Put down in writing following content TOHKEMY 2002-219319 number, that is, this pore distributes and can control through the particle diameter to the silica composition of cordierite raw material, and the kaolin low concentration is controlled.
Japanese kokai publication sho 61-129015 number following filter for exhaust gas decontamination is disclosed; Promptly; At least the surface that imports passage side of next door possesses that macropore by the aperture of aperture 5～40 μ m and aperture 40～100 μ m constitutes and the quantity of aperture is 5～40 times of quantity of macropore; And with the surperficial pore that the inner inner pore in next door is communicated with, how all the seizure collection efficiency use age of the particulate of this filter for exhaust gas decontamination constant and keep higher value.
TOHKEMY 2003-40687 number following ceramic honeycomb structure is disclosed; Promptly; With the cordierite is principal component, and the porosity is 55～65%, and average fine pore is 15～30 μ m; The gross area of the pore of next door surface opening is more than 35% of the gross area on surface, next door, can reach the lower pressure loss and higher seizure collection efficiency through this ceramic honeycomb structure.
The exhaust emission control filter of the following ojosa with pottery system is disclosed for TOHKEMY 2002-355511 number; This ojosa has the catalyst that the next door surface supports; The porosity in next door is 55～80%; The gross area of the pore of next door surface opening is more than 20% of the gross area on surface, next door; This exhaust emission control filter can make the contact area of the PM of catalyst that the next door supports and accumulation increase, and has raising based on the effect of the oxidation reaction ability of the PM of catalyst and suppress the effect that the pressure loss increases.
TOHKEMY 2002-349234 number following exhaust emission control filter is disclosed; That is, supported catalyst, the total area of the perforate of next door surface opening is more than 30% of whole surface area in next door; Opening directly is that the total area of the aperture area of the above large opening of 30 μ m is more than 50% of whole aperture areas of said perforate; Through possessing this structure, can increase substantially the oxidizing fire efficient of PM, and prevent the breakage that causes because of thermal stress.
Yet; Though the seizure of the PM of the exhaust emission control filter of record is collected performance and is uprised when piling up to a certain degree at PM in the special table of Japan 2005-530616 number, TOHKEMY 2002-219319 number, japanese kokai publication sho 61-129015 number, TOHKEMY 2003-40687 number, TOHKEMY 2002-355511 number and TOHKEMY 2002-349234 number; But; State before the PM that uses the beginning initial stage piles up (when ceramic honeycomb filter when unused state begins to be used, when perhaps after Regeneration Treatment, being used again) down may not be abundant.The seizure collection efficiency of the PM of the nano-scale that especially is much accounted of along with the reinforcement that waste gas is limited is insufficient, exists at large the catching of PM of harmful nano-scale to collect and the problem of direct discharge.
In order to address these problems; TOHKEMY 2004-360654 number following ceramic honeycomb filter is disclosed; That is, the porosity in next door is 55～75%, and average fine pore is 15～40 μ m; The gross area of the pore of next door surface opening be next door surface the gross area 10～30%, in the pore of next door surface opening, diameter of equivalent circle is that the pore of 5～20 μ m is with 300/mm 2Above state exists.Yet even the ceramic honeycomb filter of TOHKEMY 2004-360654 number record, the use after ceramic honeycomb filter regeneration begins the initial stage, and PM seizure collection efficiency is low, and this problem also is not resolved.
On the other hand; Have the method for the porous ceramic tectosome of the stable porosity as manufacturing, disclosing for TOHKEMY 2007-45686 number average grain diameter is that 10～50 μ m, the porosity are the technology that 50～90% porous matter resin particle uses as the pore-creating material.Put down in writing following content TOHKEMY 2007-45686 number; Promptly; Little and the porous matter resin particle be difficult to conquassation than hollow-particle of caloric value in the time of will burning till than solid particle uses as the pore-creating material, and thus, the shaping raw material that can suppress pore-creating material particle is mixing the excessive heating that mixes the conquassation when rubbing and burning till when; The porous ceramic tectosome that consequently, can have the stable porosity with good yield rate manufacturing.Yet, under the situation that porous matter resin particle is used as the pore-creating material, because pore-creating material particle frictional resistance each other, so when extrusion molding, need higher pressure, the undesirable condition that formed body after the generation extruding sometimes or mould deform.
Summary of the invention
[brief summary of the invention]
[problem that invention will solve]
The PM that the object of the present invention is to provide the use that can improve after ceramic honeycomb filter is regenerated to begin the initial stage catches collection rate and can reduce PM ceramic honeycomb structure and the manufacturing approach thereof that the pressure loss when being captured collection rises.
[being used to solve the means of problem]
Be that ceramic honeycomb structure of the present invention has a plurality of streams that the next door by porous matter is separated, it is characterized in that,
The porosity in said next door is 40～60%,
The aperture area rate of the pore of surperficial upper shed in said next door (total aperture area of the pore of the per unit area upper shed on surface, next door) is more than 15%,
Under the situation of the opening footpath of the pore of said next door surface upper shed by diameter of equivalent circle (having and the aperture area of pore diameter of a circle) expression with homalographic; Intermediate value opening under the area benchmark of the pore of said opening directly is more than the 10 μ m and less than 40 μ m
Said diameter of equivalent circle is that 10 μ m are above and be 350/mm less than the pore density of 40 μ m 2More than,
Said diameter of equivalent circle is that 10 μ m are above and be 1～2 less than the mean value of the circularity of the pore of 40 μ m.
The darcy infiltration coefficient in said next door is preferably 0.1 * 10 -12～2 * 10 -12m 2
Intermediate value fine pore when measuring the fine pore in said next door through mercury penetration method is more than the 5 μ m and less than 20 μ m,
Fine pore is below 10% of whole pore volume less than the pore volume of 2 μ m,
The above pore volume of fine pore 40 μ m is below 10% of whole pore volume,
Pore distribution bias σ is preferably below 0.5.
Wherein, σ=log (D20)-log (D80); The curve of the relation of expression fine pore and accumulation pore volume (will be the pore volume accumulation in footpath after value) from the fine pore of maximum to specific porous; D20 representes to be equivalent to the fine pore (μ m) under 20% the pore volume of whole pore volume, and the same expression of D80 is equivalent to the fine pore (μ m) under 80% the pore volume of whole pore volume, and D80＜D20.
The waste gas inflow side of the preferred said stream of ceramic honeycomb structure or waste gas outflow side are alternately sealed and are used as filter.
Average next door thickness is preferably 9.0～12mil, and average bee-hole density is preferably 150～300cpsi.
Thermal coefficient of expansion between 20～800 ℃ of said ceramic honeycomb structure is preferably 13 * 10 -7/ ℃ below.
The method of the present invention that will contain the base soil extrusion molding of cordierite raw material and pore-creating material and make cellular ceramic structural body is characterised in that,
Said cordierite raw material contains the silica of 15～25 quality %,
The average grain diameter of said silica is 20～30 μ m, and the particle below the particle diameter 10 μ m is below the 5 quality %, and the above particle of particle diameter 100 μ m is below the 5 quality %, and size distribution deviation SD is below 0.5, and sphericity is more than 0.5,
The amount of said pore-creating material is 5～40 quality % with respect to the cordierite raw material,
The average grain diameter of said pore-creating material is 15～50 μ m, and the particle below the particle diameter 5 μ m is below the 10 quality %, and the above particle of particle diameter 80 μ m is below the 5 quality %, and size distribution deviation SD is below 0.5, and sphericity is more than 0.5.
Wherein, SD=log (d80)-log (d20); In the curve of the relation of representing particle diameter and cumulative volume (with the value after the accumulation of the particle volume below the specific particle diameter); D20 representes to be equivalent to the particle diameter (μ m) under 20% the cumulative volume of whole volumes, and the same expression of d80 is equivalent to the particle diameter (μ m) under 80% the cumulative volume of whole volumes, and d20＜d80.
Said pore-creating material is preferably porous matter polymer, and said pore-creating material particle preferably has more than 30% and less than 50% space.
The space of preferred said pore-creating material particle contain moisture more than 80%.
Preferably: the talcum that in said cordierite raw material, contains 40～43 quality %; The average grain diameter of said talcum is 1～10 μ m; In the curve of the relation of representing particle diameter and cumulative volume (with the value after the accumulation of the particle volume below the specific particle diameter); The particle diameter d90 that is equivalent under 90% the cumulative volume of whole volumes is below the 30 μ m, and size distribution deviation SD is below 0.7.
The shape factor of representing the dull and stereotyped degree of said talcum particle is preferably more than 0.77.
[invention effect]
According to ceramic honeycomb structure of the present invention; Not only can keep the lower pressure loss but also seizure after can making regeneration is collected the PM at beginning initial stage and caught collection rate and improve; Therefore; Especially can catch effectively and collect the reinforcement of following the waste gas restriction and the PM of the nano-scale that is much accounted of, thereby can solve the problem of the PM that discharges harmful nano-scale.
Description of drawings
Fig. 1 is the front view of an example of expression ceramic honeycomb filter.
Fig. 2 is the schematic cross sectional views of an example of expression ceramic honeycomb filter.
Fig. 3 is the curve map of relation of diameter of equivalent circle and accumulation area of pore that is shown schematically in the next door surface opening of ceramic honeycomb structure.
Fig. 4 is the curve map of relation of fine pore and pore volume of the ceramic honeycomb structure of expression embodiment 11.
Fig. 5 is the curve map of the size distribution of the silica E that uses in the embodiments of the invention of expression.
Fig. 6 is the electron micrograph of an example of expression silicon dioxide granule.
Fig. 7 is the electron micrograph on surface in next door of the ceramic honeycomb structure of expression embodiment 11.
Fig. 8 is the electron micrograph in cross section in next door of the ceramic honeycomb structure of expression embodiment 11.
The specific embodiment
[1] ceramic honeycomb structure
(1) structure
Ceramic honeycomb structure of the present invention has a plurality of streams of being separated by the next door of porous matter, it is characterized in that,
The porosity in said next door is 40～60%,
The aperture area rate of the pore of surperficial upper shed in said next door (total aperture area of the pore of the per unit area upper shed on surface, next door) is more than 15%,
Under the situation of the opening footpath of the pore of said next door surface upper shed with diameter of equivalent circle (having diameter of a circle) expression with the equal area of the aperture area of pore; Intermediate value opening under the area benchmark of the pore of said opening directly is more than the 10 μ m and less than 40 μ m
Said diameter of equivalent circle is that 10 μ m are above and be 350/mm less than the pore density of 40 μ m 2More than,
Said diameter of equivalent circle is that 10 μ m are above and be 1～2 less than the mean value of the circularity of the pore of 40 μ m.Through possessing this structure, ceramic honeycomb structure of the present invention can improve use after the regeneration and begin the PM at initial stage and catch collection rate, and can reduce the be captured rising of the pressure loss when collecting of PM.
(i) porosity
The porosity of next door is less than under 40% the situation, and the pressure loss becomes greatly, can't when PM be captured collection, keep low pressure loss characteristic, and on the other hand, if the porosity surpasses 60%, then the use after the regeneration begins the PM seizure collection rate decline at initial stage.The porosity in next door is preferably 43～57%, further is preferably 45～55%.
(ii) aperture area rate
The aperture area rate of the pore of next door surface opening is total aperture area of the pore of the surperficial per unit area upper shed in next door.The aperture area rate can be calculated through following mode; Promptly; In the electron micrograph that the surface of counter septum is taken; Utilize image analysis apparatus (for example, the system Image-Pro Plus ver.3.0 of Media Cybernetics society) to obtain the total amount of the aperture area of each pore, and should the total amount calculate divided by measuring visual field area.
The aperture area rate less than 15% situation under, be difficult to be captured and keep the lower pressure loss when collecting at PM.On the other hand, the PM that begins the initial stage for the use after preventing to regenerate catches collection rate and descends, and the aperture area rate is preferably below 40%.Said aperture area rate further is preferably 18～38%.
(iii) the intermediate value opening directly
As shown in Figure 3; For the footpath of the intermediate value opening under the area benchmark of the pore of opening; With respect to diameter of equivalent circle (having and the aperture area of pore diameter of a circle) with homalographic; In with the curve map after the accumulation area of the pore of next door surface upper shed (value after aperture area that will the pore specific diameter of equivalent circle below the is accumulated) curveization, said intermediate value opening directly is the diameter of equivalent circle that becomes the pore of 50% the accumulation area that is equivalent to whole pore areas.The electron micrograph that the aperture area of intermediate value opening footpath, pore and diameter of equivalent circle can be taken through the surface that utilizes image analysis apparatus (for example, Media Cybernetics society system Image-Pro Plus ver.3.0) to analyze counter septum and obtaining.
Under the situation of intermediate value opening footpath less than 10 μ m, can't be captured at PM and keep lower pressure loss characteristic when collecting, on the other hand, when the intermediate value opening directly is under the situation more than the 40 μ m, the PM that the use after the regeneration begins the initial stage catches collection rate and reduces.Said intermediate value opening directly is preferably 15～35 μ m.
(iv) pore density
The diameter of equivalent circle of the pore of next door surface opening is that 10 μ m are above and be meant less than the pore density of 40 μ m, in the pore of the per unit area upper shed on surface, next door, diameter of equivalent circle is that 10 μ m are above and less than the quantity of the pore of 40 μ m.
At said diameter of equivalent circle is for less than 350/mm more than the 10 μ m and less than the pore density of 40 μ m 2Situation under, the PM that the use after the regeneration begins the initial stage catches collection rate and descends.Said pore density is preferably 400/mm 2More than.
(v) circularity
At said diameter of equivalent circle is to surpass under 2 the situation more than the 10 μ m and less than the mean value of the circularity of the pore of 40 μ m, is difficult to be captured at PM keep the lower pressure loss when collecting, and the PM that the use after the regeneration begins the initial stage catches collection rate and reduces.The mean value of said circularity is preferably 1～1.5.Need to prove, circularity by have with aperture area be that the ratio of area A 1 and the aperture area A0 of pore of the circle of the equal circumferential length of the contour length (L) of the pore of A0 is A 1/ A 0Expression, it is the value more than 1.
(vi) darcy infiltration coefficient
The darcy infiltration coefficient in the next door of ceramic honeycomb structure is preferably 0.1 * 10 -12～2 * 10 -12m 2Through having said darcy infiltration coefficient, the initial stage pressure loss in the time of can the use after the regeneration being begun is kept lowly, not only can improve use after the regeneration and begin the PM at initial stage and catch collection rate, and the pressure loss that PM is captured when collecting also reduces.At the darcy infiltration coefficient less than 0.1 * 10 -12m 2Situation under, be difficult to keep the initial stage pressure loss of the use after the regeneration when beginning low.On the other hand, surpass 2 * 10 when the darcy infiltration coefficient -12m 2Situation under, exist PM catch to collect performance and become bad situation.The darcy infiltration coefficient is preferably 0.2 * 10 -12～1.5 * 10 -12m 2
(vii) fine pore and pore distribute
Intermediate value fine pore when measuring the fine pore in next door of ceramic honeycomb structure through mercury penetration method is more than the 5 μ m and less than 20 μ m; Fine pore is below 10% of whole pore volume less than the pore volume of 2 μ m; Fine pore is that the above pore volume of 40 μ m is below 10% of whole pore volume, and pore distribution bias σ is preferably below 0.5.Through possessing this pore structure, the initial stage pressure loss in the time of can the use after the regeneration being begun is kept lowly, not only can improve use after the regeneration and begin the PM at initial stage and catch collection rate, but also can reduce the PM pressure loss when collecting that is captured.
At this; Pore distribution bias σ is log (D20)-log (D80); As shown in Figure 4; The curve of the relation of fine pore that expression is measured through mercury penetration method and accumulation pore volume (will from the fine pore of maximum to the pore volume accumulation in specific porous footpath after value), D20 representes to be equivalent to the fine pore (μ m) under 20% the pore volume of whole pore volume, and D80 representes to be equivalent to the fine pore (μ m) under 80% the pore volume of whole pore volume equally.D80＜D20。
Under the situation of said intermediate value fine pore less than 5 μ m, be difficult to keep the initial stage pressure loss of the use after the regeneration when beginning low.On the other hand, be under the situation more than the 20 μ m in said intermediate value fine pore, there is following situation, that is, it is to tail off more than the 5 μ m and less than the pore volume of 20 μ m that PM catch is collected effective fine pore, PM catches and collects performance and become bad.Said intermediate value fine pore is preferably 7～18 μ m.
Fine pore has the effect that the pore bigger than its aperture is communicated with less than the pore of 2 μ m, thereby improves initial stage pressure loss characteristic.If fine pore surpasses 10% less than the pore volume of 2 μ m, though can guarantee the connectedness of pore, the ratio that fine pore surpasses the pore of 2 μ m tails off relatively, thereby is difficult to keep the initial stage pressure loss low.On the other hand, under the fine pore situation very few less than the pore of 2 μ m, the initial stage pressure loss becomes big owing to can not fully guarantee the connectedness of pore, so fine pore is preferably 1～8% less than the pore volume of 2 μ m.
Fine pore be pore volume more than the 40 μ m surpass whole pore volume 10% situation under, have following situation, that is, PM caught to collect effective fine pore be to tail off more than the 5 μ m and less than the pore volume of 20 μ m, PM catches and collects performance and become bad.Fine pore is that the above pore volume of 40 μ m is preferably below 8%.
Fine pore is below 10% less than the pore volume of 2 μ m; Fine pore is that the above pore volume of 40 μ m is below 10%; Pore distribution bias σ is 0.5 when following, and the intermediate value fine pore is that 5 μ m are above and less than the increasing proportion of the pore of 20 μ m, pore distribution narrow.The next door of this structure has the lower initial stage pressure loss, but if pore distribution bias σ surpasses 0.5, then initial stage pressure loss characteristic is brought the increasing proportion of dysgenic pore, is difficult to keep the lower initial stage pressure loss.Pore distribution bias σ is preferably below 0.45, further is preferably below 0.4.
(viii) ojosa
Preferably in the scope of 9.0～12mil, average bee-hole density is preferably in the scope of 150～300cpsi for the average next door thickness of ceramic honeycomb structure.Through having this ojosa, the initial stage pressure loss in the time of can the use after the regeneration being begun is kept lowly, not only can improve use after the regeneration and begin the PM at initial stage and catch collection rate, and can reduce the PM pressure loss when collecting that is captured.Under the average situation of next door thickness less than 9.0mil (0.229mm), the intensity in next door descends, and on the other hand, thickness surpasses under the situation of 12mil (0.305mm) in average next door, is difficult to keep the lower pressure loss.In average bee-hole density less than 150cpsi (23.3 bee-holes/cm 2) situation under, the intensity in next door descends, and on the other hand, surpasses 300cpsi (46.5 bee-holes/cm in average bee-hole density 2) situation under, be difficult to keep the pressure loss of reduction.
(2) thermal coefficient of expansion
Thermal coefficient of expansion between 20～800 ℃ of ceramic honeycomb structure is preferably 13 * 10 -7/ ℃ below.Through having this thermal coefficient of expansion, when ceramic honeycomb structure is used as the ceramic honeycomb filter of the contained particulate of the waste gas that is used for removing diesel engine, can keep resistance to sudden heating, can keep the intensity of withstanding actual use.Thermal coefficient of expansion is preferably 3 * 10 -7～11 * 10 -7/ ℃.
(3) material
Because intended use is to be used for the waste gas of discharging from Diesel engine is carried out filter purifying; So the next door that constitutes ceramic honeycomb structure is preferably by having stable on heating pottery; Promptly; With aluminium oxide, mullite, cordierite, carborundum, silicon nitride, zirconia, aluminium titanates, lithium aluminosilicate etc. is the pottery formation of primary crystallization, especially, and preferably by constituting at the cordierite of low-thermal-expansion superior aspect the resistance to sudden heating, the pottery that aluminium titanates is primary crystallization.At principal crystalline phase is under the situation of cordierite, also can contain spinelle, mullite, sapphirine (サ Off イ リ Application) and wait other crystalline phases, can further contain glass ingredient.
(4) ceramic honeycomb filter
For ceramic honeycomb structure of the present invention; Through alternately sealing into the waste gas inflow side and the waste gas outflow side of said stream latticed; Thereby form following ceramic honeycomb filter, that is, the initial stage pressure loss in the time of can the use after the regeneration being begun is kept lowly; Not only can improve use after the regeneration and begin the PM at initial stage and catch collection rate, but also can reduce the PM pressure loss when collecting that is captured.At this; As long as waste gas inflow side and waste gas outflow side are alternately sealed into latticed; Then be formed at sealing of stream and need not necessarily to be formed on the end face portion of stream, also can be formed on the position that from inflow side end face or outflow side end face get into the inside of honeycomb structure.
[2] manufacturing approach of ceramic honeycomb structure
Make in the method for the present invention of cellular ceramic structural body at the base soil extrusion molding that will contain cordierite raw material and pore-creating material, it is characterized in that
Said cordierite raw material contains the silica of 15～25 quality %,
The average grain diameter of said silica is 20～30 μ m, and particle diameter is that the particle below the 10 μ m is below the 5 quality %, and particle diameter is that the above particle of 100 μ m is below the 5 quality %, and size distribution deviation SD is below 0.5, and sphericity is more than 0.5,
The amount of said pore-creating material is 5～40 quality % with respect to the cordierite raw material,
The average grain diameter of said pore-creating material is 15～50 μ m, and particle diameter is that the particle below the 5 μ m is below the 10 quality %, and particle diameter is that the above particle of 80 μ m is below the 5 quality %, and size distribution deviation SD is below 0.5, and sphericity is more than 0.5.
At this; The size distribution deviation SD of silicon dioxide granule and pore-creating material particle is by SD=log (d80)-log (d20) expression; As shown in Figure 5; In the curve of the relation of expression particle diameter and cumulative volume (value after will the particle volume specific particle diameter below accumulating), d20 representes to be equivalent to the particle diameter (μ m) under 20% the cumulative volume of whole volumes, and d80 representes to be equivalent to the particle diameter (μ m) under 80% the cumulative volume of whole volumes equally.Need to prove d20＜d80.Granularity for example can use day machine dress (strain) system Microtrack particle size distribution device (MT3000) to measure.About the average grain diameter of silicon dioxide granule and pore-creating material particle, median particle diameter (d50) is represented by the particle diameter under 50% the cumulative volume that is equivalent to whole volumes in the curve of the relation of expression aforesaid particle diameter and cumulative volume.In this application, only if special negate outside, also be likewise to define size distribution deviation SD and average grain diameter to other particles.
According to the method for the invention; Can obtain following ceramic honeycomb structure; Be characterised in that; Have a plurality of streams that the next door by porous matter is separated; The porosity in said next door is 40～60%, and the aperture area rate of the pore of surface opening in said next door (total aperture area of the pore of the per unit area upper shed on next door surface) is more than 15%, under the situation by diameter of equivalent circle (having and the aperture area of the pore diameter of a circle with homalographic) expression of the opening footpath of the pore of said next door surface upper shed; Intermediate value opening under the area benchmark of the pore of said opening directly is that 10 μ m are above and less than 40 μ m, and said diameter of equivalent circle is that 10 μ m are above and be 350/mm less than the pore density of 40 μ m 2More than, said diameter of equivalent circle is that 10 μ m are above and be 1～2 less than the mean value of the circularity of the pore of 40 μ m.
(chemical composition of principal component is the SiO of 42～56 quality % in order to make primary crystallization become cordierite 2, the Al of 30～45 quality % 2O 3And the MgO of 12～16 quality %), the cordierite raw material need cooperate have the silica derived components, each material powder of alumina source composition and magnesium oxide source composition.With the cordierite be silica and talcum that the pore that forms on the pottery of primary crystallization is based on the cordierite raw material burnt till the pore that produces and pore-creating material by burning produce pore produced.
Wherein, because silica and pore-creating material are favourable for the major part of formed pore, so, regulate through average grain diameter and size distribution them, can control the pore that cordierite ceramic produces when burning till.Therefore; Through adopting use amount, average grain diameter and size distribution to be in silica and pore-creating material in the aforementioned range; Can obtain following ceramic honeycomb structure, that is, it is formed with the next door with desirable pore structure; Not only can improve use after the regeneration and begin the PM at initial stage and catch collection rate, but also the pressure loss that PM is captured when collecting reduces.
(1) silicon dioxide granule
As everyone knows, silica is compared with other raw materials at high temperature also can stable existence, and it forms pore in fusion diffusion more than 1300 ℃.For this reason, if contain the silica of 15～25 quality %, then can obtain the pore of desired amount.If contain the silica that surpasses 25 quality %; For primary crystallization is maintained cordierite; Must reduce kaolin, talcum as other silica derived components; The effect of the low-thermal-expansionization that consequently, obtains through kaolin (the directed effect that obtains of kaolin when making extrusion molding) reduces resistance to sudden heating decline.On the other hand, silica less than 15% situation under because the amount of the pore of next door surface upper shed reduces, obtain the situation of lower pressure loss characteristic when collecting so exist to be captured at PM.The amount of silica is preferably 17～23%.
Under the situation of average grain diameter less than 20 μ m of silica, in the pore of next door surface upper shed, catch the increasing proportion that lower pressure loss characteristic when collecting is brought dysgenic small pore for keeping PM.On the other hand, surpass under the situation of 30 μ m in the average grain diameter of silica, the thick pore that the PM that makes use after the regeneration begin the initial stage catches the collection rate deterioration increases.The average grain diameter of silica is preferably 22～28 μ m.
Under the particle below the particle diameter 10 μ m of silica surpasses the situation of 5 quality %, in the pore of next door surface upper shed, keep the increasing proportion that lower pressure loss characteristic is brought dysgenic small pore when collecting for being captured at PM.The particle diameter of silica is that the ratio of the particle below the 10 μ m is preferably below the 3 quality %.
Under the particle more than the particle diameter 100 μ m of silica surpassed the situation of 5 quality %, the thick pore that the PM that makes use after the regeneration begin the initial stage catches the collection rate deterioration increased, and the PM that exists use after the regeneration to begin the initial stage catches and collects performance and become bad situation.The ratio of the particle that the particle diameter 100 μ m of silica are above is preferably below the 3 quality %.
Be in the average grain diameter of silicon dioxide granule that 20～30 μ m, particle diameter are that particle below the 10 μ m is below the 5 quality %, particle diameter is that particle more than the 100 μ m is under the situation below the 5 quality %; Size distribution deviation SD through making silicon dioxide granule is below 0.5, and PM in the pore that forms on the next door surface, that do not make use after the regeneration begin the initial stage catches the collection rate deterioration but PM caught the increasing proportion of keeping the pore that low pressure loss contributes when collecting.
If size distribution deviation SD surpasses 0.5, then size distribution becomes wide, and formed pore distributes and also becomes wide.Therefore, catch the increasing proportion that collection rate and pressure loss characteristic are brought dysgenic pore for PM, the PM that the use after the regeneration begins the initial stage catches collection rate and descends, and can't be captured at PM and keep the lower pressure loss when collecting.Size distribution deviation SD is preferably below 0.45, further is preferably below 0.4.The mixing of a plurality of silicon dioxide granules that have classification that silicon dioxide granule that the particle diameter of the expectation of aforementioned that kind distributes can be through utilizing the silicon dioxide granule that grading plant carries out, are classified as several particle diameters or the optimization of pulverization conditions obtain.
Silicon dioxide granule uses the particle of the sphericity more than 0.5.The sphericity of silicon dioxide granule less than 0.5 situation under; The circularity of the pore of next door surface upper shed becomes big; The PM that makes use after the regeneration begin the initial stage catches the thick pore of collecting deterioration to be increased, and brings dysgenic small pore to increase for keeping the lower pressure loss characteristic that PM is captured when collecting simultaneously.The sphericity of silicon dioxide granule is preferably more than 0.6, further is preferably more than 0.7.The sphericity of silicon dioxide granule is; With the projected area of silicon dioxide granule divided by the area of maximum as the circle of diameter of 2 the straight line that links the particle periphery with the center of gravity of having passed through silicon dioxide granule after resulting value, can utilize image analysis apparatus to obtain from electron micrograph.
Said silicon dioxide granule can be the particle of crystalline, also can be amorphous particle, but considers preferred amorphous particle from the viewpoint of adjustment size distribution.Amorphous silica can be pulverized through the ingot bar that highly purified natural silica high-temperature fusion is made and obtain.Silicon dioxide granule can contain the Na as impurity 2O, K 2O and CaO become big in order to prevent thermal coefficient of expansion, and the amount of said impurity preferably adds up to below 0.1%.
The high silicon dioxide granule of sphericity can through with highly purified natural silica micro mist broken and in thermal-flame meltallizing obtain.Carry out the fusion and the spheroidizing of silicon dioxide granule simultaneously through the meltallizing in thermal-flame, thereby can obtain spherical amorphous silica shown in Figure 6.This spherical silicon dioxide particle preferably further carries out the granularity adjustment through methods such as classifications.
(2) pore-creating material
The pore-creating material contains 5～40 quality % with respect to the cordierite raw material, and in the sintering process of cordierite ceramic, it burns before cordierite is synthesized and disappears and the formation pore.Under the situation of amount less than 5 quality % of pore-creating material,,, PM can't keep lower pressure loss characteristic when being captured collection owing to reduce through the pore amount of pore-creating material formation.If the PM that the amount of pore-creating material above 40 quality %, then makes the use after the regeneration begin the initial stage catches the increasing proportion of the pore of collection rate deterioration.The amount of pore-creating material is preferably 5～15 quality %, and then is preferably 7～13 quality %.
The average grain diameter of pore-creating material particle is 15～50 μ m.Under the situation of average grain diameter less than 15 μ m, the pore that helps to keep lower pressure loss characteristic reduces, and the pressure loss rises when PM is captured collection.If the average grain diameter of pore-creating material particle surpasses 50 μ m, then formed pore becomes thick, and therefore, the PM that makes use after the regeneration begin the initial stage catches the increasing proportion of the pore of collection rate deterioration.The average grain diameter of pore-creating material particle is preferably 17～45 μ m.
The size distribution deviation SD of pore-creating material is below 0.5.Size distribution deviation SD through making the pore-creating material is below 0.5; Because formed pore distribution narrow; Therefore, help to be captured and keep increasing proportion lower pressure loss characteristic, that can catch the pore of the PM that use after collecting regeneration begins the initial stage when collecting at PM.Consequently; Can obtain to form the porous matter next door with vesicular structure of putting down in writing among the present invention, the use after not only when PM is captured collection, keeps the lower pressure loss but also make regeneration begins the PM at initial stage and catches the improved ceramic honeycomb structure of collection rate.
If the size distribution deviation SD of pore-creating material surpasses 0.5, then size distribution becomes wide, and formed pore distributes and also becomes wide.Therefore, PM is caught the increasing proportion that collection rate and pressure loss characteristic are brought dysgenic pore, the PM that the use after the regeneration begins the initial stage catches collection rate and descends, and can't be captured at PM and keep the lower pressure loss when collecting.The size distribution deviation SD of pore-creating material is preferred below 0.4, further is preferably below 0.35.
Pore-creating material particle uses the particle of the sphericity more than 0.5.The sphericity of pore-creating material particle less than 0.5 situation under; The circularity of the pore of next door surface upper shed becomes big; The PM that not only makes use after the regeneration begin the initial stage catches the thick pore of collecting deterioration to be increased, and keeps lower pressure loss characteristic when collecting for being captured at PM and bring dysgenic small pore to increase.The sphericity of pore-creating material particle is preferably more than 0.7, further is preferably more than 0.8.Need to prove that the sphericity of pore-creating material particle can likewise be obtained with silicon dioxide granule.
For the pore-creating material; As long as its average grain diameter and size distribution deviation SD are in aforesaid scope; Then unqualified to its material, can with graphite, wheat flour, starch, Foamex, accomplish Foamex, accomplish foaming hollow resin, cramic coat resin, cramic coat hollow resin, porous matter polymer etc. and do not use as the pore-creating material.
In the manufacturing approach of ceramic honeycomb structure of the present invention, said pore-creating material particle is a porous matter polymer, and said pore-creating material particle preferably has more than 30% and less than 50% space, further is preferably to contain moisture more than 80% in said space.Pore-creating material particle be porous matter polymer and have more than 30% and situation less than 50% space under; Combustion heating amount when burning till reduces, and is difficult for when burning till, cracking, and pore-creating material particle is difficult for conquassation when extrusion molding; Therefore, can stably obtain the pore expected.
As the porous matter polymer that pore-creating material particle uses, preferred: resins such as (gathering) methyl methacrylate, polybutyl methacrylate, polyacrylate, polystyrene, polyacrylate.
The space of pore-creating material particle less than 30% situation under, the combustion heating amount when burning till increases, and on ceramic honeycomb structure, is easy to generate the crack.On the other hand, be under the situation more than 50% in the space of pore-creating material particle, the easy conquassation of pore-creating material particle during with shaping raw material mixing and mixed rubbing, the pore that is difficult to stably obtain to expect distributes.
Usually, if use the shaping raw material contain the pore-creating material, then because of there being pore-creating material particle frictional resistance each other, thereby extrusion molding needs higher pressure, exists the formed body after the extruding to produce the situation of distortion.Difference according to circumstances can't form because of higher pressure causes die deformation sometimes.Yet, through will the space more than 80% in contain moisture porous matter polymer use as the pore-creating material, the interparticle frictional resistance of pore-creating material reduces, and can under the situation that does not need higher squeeze pressure, realize extrusion molding.The porous matter polymer that in the space, contains moisture can use the vacuum impregnation device to process.
(3) talcum
In the manufacturing approach of ceramic honeycomb structure of the present invention; The talcum that in the cordierite raw material, contains 40～43 quality %; The average grain diameter of said talcum is 1～10 μ m; In the curve of the relation of expression particle diameter and cumulative volume (accumulate the particle volume below the specific particle diameter after value), the particle diameter d90 that is equivalent under 90% the cumulative volume of whole volumes is below the 30 μ m, and size distribution deviation SD is preferably below 0.7.
Have on the next door that silica and talcum in the cordierite raw material burns till and the pore that produces and pore-creating material combustion and the pore that produces; But; Between the pore that forms through silica and pore-creating material; Through being that the talcum particle of 1～10 μ m forms pore by the average grain diameter littler than the average grain diameter of silica and pore-creating material; The pore utilization that forms through silica and pore-creating material is communicated with through the pore that the talcum particle forms, thereby the connectedness of the pore in the next door is improved.Consequently,, keeps PM lower pressure loss characteristic when being captured collection.Especially, through using the pore-creating material of aforementioned porous matter polymer, stably obtain the pore of expectation in can next door, can stably obtain the PM lower pressure loss characteristic when collecting that is captured.Yet, under the situation of average grain diameter less than 1 μ m of talcum, be difficult to guarantee the connectedness of pore, be difficult to when PM is captured collection, obtain lower initial stage pressure loss characteristic.On the other hand, surpass under the situation of 10 μ m in the average grain diameter of talcum, the thick pore that the PM that makes use after the regeneration begin the initial stage catches the collection rate deterioration increases.The average grain diameter of talcum particle is preferably 2～8 μ m.
In the curve of the relation of particle diameter and the cumulative volume (value after the particle volume below the specific particle diameter is accumulated) of expression talcum; Particle diameter d90 being equivalent under 90% the cumulative volume of whole volumes surpasses under the situation of 30 μ m, and the thick pore that the PM that makes use after the regeneration begin the initial stage catches the collection rate deterioration increases.D90 is preferably below the 25 μ m.
Average grain diameter at the talcum particle is 1～10 μ m; In the curve of the relation of expression particle diameter and cumulative volume (with the value after the accumulation of the particle volume below the specific particle diameter); The particle diameter d90 that is equivalent under 90% the cumulative volume of whole volumes is under the situation below the 30 μ m; Size distribution deviation SD through making talcum is below 0.7; Formed pore distribution narrow, thus can keep the initial stage pressure loss of the use after the regeneration begin the time low, and can catch the increasing proportion of the pore of the PM that the use of collecting after the regeneration begins the initial stage.
If size distribution deviation SD surpasses 0.7, it is wide that size distribution becomes, and formed pore distributes and also becomes wide.Therefore, catch the increasing proportion that collection rate and pressure loss characteristic are brought dysgenic pore for PM, the PM that the use after the regeneration begins the initial stage catches collection rate and reduces, and being captured at PM is difficult to keep the lower pressure loss when collecting.Size distribution deviation SD is preferably below 0.65, further is preferably below 0.6.The mixing of a plurality of talcum particles that have classification that talcum particle that the particle diameter of the expectation of aforementioned that kind distributes can be through utilizing the talcum particle that grading plant carries out, are classified into several particle diameters or the optimization of pulverization conditions obtain.
The viewpoint of thermal coefficient of expansion that from the principal component that reduces crystalline phase is the ceramic honeycomb structure of cordierite considers that talcum is preferably tabular particle.The shape factor of the dull and stereotyped degree of expression talcum particle is preferably more than 0.77, further is preferably more than 0.8, most preferably is more than 0.83.Like United States Patent (USP) the 5th; 141; That kind of No. 686 records, said shape factor can be through carrying out X-ray diffraction under the directed state of tabular talcum particle and measure making, and pass through numerical expression according to diffracted intensity Ix of (004) face of talcum and the diffracted intensity Iy of (020) face:
Shape factor=Ix/ (Ix+2Iy)
And try to achieve.The dull and stereotyped degree of the big more talcum particle of shape factor is high more.
Talcum can contain the Fe as impurity 2O 3, CaO, Na 2O, K 2O etc.For the size distribution that obtains to expect, Fe 2O 3Containing ratio in the magnesium oxide source raw material, be preferably 0.5～2.5 quality %, consider Na from reducing the thermal coefficient of expansion this point 2O, K 2The containing ratio of O and CaO preferably adds up to below the 0.50 quality %.
(4) kaolin
As the silica source raw material, on the basis of said SiO 2 powder, can cooperate the kaolin powder.The amount of kaolin powder is preferably 1～15 quality %.If the amount of kaolin powder surpasses 15 quality %; Then exist and be difficult to the fine pore of ceramic honeycomb structure is adjusted into the situation below 10% less than the pore of 2 μ; Under the situation of amount less than 1 quality % of kaolin powder, it is big that the thermal coefficient of expansion of ceramic honeycomb structure becomes.The amount of kaolin powder further is preferably 4～8 quality %.
As if the kaolin particle being oriented the length direction quadrature of its c axle with the honeycomb structure that is extruded, then the c axle of cordierite crystallization is parallel with the length direction of honeycomb structure, thereby can reduce the thermal coefficient of expansion of honeycomb structure.The shape of kaolin particle is brought considerable influence to the orientation of the kaolin particle in the formed body.For the kaolin particle is directed with aforementioned manner, be that di (cleavage index) is preferably more than 0.80 with the index of the shape quantificational expression of kaolin particle, further be preferably more than 0.85.The orientation of the bigger then kaolin of di particle becomes good more.
The di of kaolin particle can be obtained as follows; Promptly; According to being filled into the pressurization of a certain amount of kaolin particle in the container and utilizing X-ray diffraction that each peak strength of (200) face, (020) face and (002) face of kaolin particle is measured the measured value that obtains, through following numerical expression:
Di=I (002)/ (I (200)+ I (020)+ I (002))
[in the formula, I (200), I (020)And I (002)Be respectively the value of each peak strength of (200) face, (020) face, (002) face of the kaolin particle of measuring through X-ray diffraction] obtain.
(5) alumina source raw material
As the alumina source raw material, preferred aluminium oxide and/or aluminium hydroxide on the few this point of impurity.Impurity in aluminium oxide and the aluminium hydroxide is Na 2O, K 2The amount total of O and CaO is preferably below the 0.5 quality %, more preferably below the 0.3 quality %, most preferably is below the 0.1 quality %.Use the amount of the aluminium hydroxide in the cordierite raw material under the aluminium hydroxide situation to be preferably 6～42 quality %.Use the amount of the aluminium oxide in the cordierite raw material under the aluminium oxide situation to be preferably below the 35 quality %.
(6) manufacturing approach
To adjustment in the above described manner, cordierite material powder and pore-creating material add adhesive and add additive such as dispersant, interfacial agent as required and after carrying out dry mixed; Adding entry mixes and rubs and process the base soil (at said additive is under the situation of liquid, also can add mixing when rubbing) of plasticization.Utilize the mould of known ojosa shaping usefulness, form the formed body of ojosa through this base soil of known extruding formation method extruding.After the formed body that is obtained is carried out drying, as required end face and periphery etc. is processed, burn till the acquisition ceramic honeycomb structure then.
Burn till as follows and carry out, that is, use continuous oven or batch furnace, heat up, between 1350～1450 ℃, kept 1～50 hour, after fully generating the cordierite primary crystallization, be cooled to room temperature while regulating the speed.Especially for external diameter be more than the 150mm, total length is for the large size ceramic honeycomb structure more than the 150mm; Do not chap in order in sintering process, on ceramic honeycomb structure, not produce; Said programming rate is 0.2～10 ℃/hr under 150～350 ℃ for example in temperature range that adhesive decomposes, is 5～20 ℃/hr under 1150～1400 ℃ for example in temperature province that the cordierite reaction is carried out.Especially preferably in 1400～1300 ℃ scope, cool off with the speed of 20～40 ℃/h.
With known method the honeycomb structure that obtained being formed that mouth-sealed portion forms is the ceramic honeycomb filter that the end of stream of expectation is sealed.Need to prove that this mouth-sealed portion also can burn till preceding formation.
In manufacturing approach of the present invention, as aforementioned, be vital to the size distribution adjustment of silica, talcum, pore-creating material.Therefore; In the present invention; Preferably after in the cordierite raw material that is made up of silicon dioxide granule, talcum particle, kaolin particle, aluminium oxide particles etc., adding pore-creating material and adhesive, the method for utilizing Henschel mixer etc. not contain crushing medium is mixed, then after adding entry; The method that does not apply excessive shear through kneading machine etc. is mixed and is rubbed, thereby processes the base soil of the plasticization that extrusion molding uses.
Method through not containing crushing medium is mixed; Can prevent silicon dioxide granule especially the amorphous silica particle pulverized in mixed process, can make in the formed body after the silicon dioxide granule of size distribution with expectation and shape of particle is present in extrusion molding with maintaining the original state.Therefore, can obtain when keeping low pressure loss, the PM that the beginning initial stage is collected in the seizure after the regeneration catches the improved ceramic honeycomb structure of collection rate.Especially, under the situation of using spherical silicon dioxide, adopt the effect of said mixed method obvious.In mixed processes, adopt ball mill etc. to have under the situation of mixed method of crushing medium, silicon dioxide granule especially spherical silicon dioxide particle is pulverized in mixed process, and its shape and particle diameter change, so not preferred.
Below, embodiment of the present invention is carried out detailed explanation.
SiO 2 powder, kaolin powder, talcum powder, alumina powder and the aluminium-hydroxide powder that will have the shape of particle shown in table 1～table 4 (particle diameter, size distribution etc.) cooperate with the addition shown in the table 6, are the SiO of 50 quality % thereby obtain chemical composition 2, 35 quality % Al 2O 3And the cordierite material powder of the MgO of 13 quality %.This cordierite material powder is being added the pore-creating material of the shape of particle shown in the table 5 with the amount shown in the table 6, and after adding methylcellulose, adding water and mix and rub, thereby process by having the ceramic base soil that plastic cordierite raw material constitutes.Need to prove that pore-creating materials A～M makes through the vacuum impregnation device and contains immersion in the space of each porous matter polymer and use.To in the space of porous matter polymer, represent with the mode of moisture content by the volume of shared water in the table 5.
The base soil that is obtained is crushed to the formed body of ojosa, after drying, circumference is removed processing, in firing furnace, burn till with 200 hours schedule.Wherein, in 150～350 ℃ and 1150～1400 ℃, respectively with the speed intensification of 2 ℃/hr and 10 ℃/hr, keep 24hr down for 1410 ℃ in maximum temperature, the speed with 30 ℃/hr in 1400～1300 ℃ is cooled off.The periphery of the ceramic honeycomb body after burning till covers the crust material that is made up of amorphous silica and cataloid and makes its drying, obtains external diameter 266.7mm and the embodiment 1～26 with the bee-hole spacing shown in the table 7 and next door thickness of total length 304.8mm and the ceramic honeycomb structure of comparative example 1～9.The surface, next door of the ceramic honeycomb structure of embodiment 11 and the electron micrograph in cross section are respectively like Fig. 7 and shown in Figure 8.
The size distribution of SiO 2 powder and talcum powder uses day machine dress (strain) system Microtrack particle size distribution device (MT3000) to measure, thereby obtains ratio, above ratio and the size distribution deviation of 100 μ m below average grain diameter (median particle diameter d50), the particle diameter 10 μ m.The sphericity of silicon dioxide granule is the value of calculating as follows; Promptly; According to the projected area A1 that utilizes image analysis apparatus to obtain from the image of the particle that photographs through electron microscope with to have passed through center of gravity and to be the area A 2 of the circle of diameter with the maximum of the straight line of 2 bindings of particle periphery; Utilize numerical expression: the value that A1/A2 calculates, its mean value with 20 particles is represented.
The joint filling material slurry that is made up of the cordierite raw material is filled in stream end at said ceramic honeycomb structure with the mode of alternately sealing; Carry out the dry of joint filling material slurry then and burn till, thereby process each cordierite ceramic honeycomb filter of embodiment and comparative example.The length of the joint filling material after burning till is the scope of 7～10mm.Each ceramic honeycomb filter respectively process respectively two identical.
To 1 ceramic honeycomb filter in the ceramic honeycomb filter of embodiment that is obtained 1～26 and comparative example 1～9, carried out mensuration and the mensuration of darcy infiltration coefficient of quantity of the pore of next door surface upper shed.The result is as shown in table 7.
Aperture area rate about the pore of next door surface upper shed; Utilize image analysis apparatus (Media Cybernetics society system Image-Pro Plus ver.3.0) that the electron micrograph on the surface in the next door that cuts out from amplifier case is analyzed, thereby obtained with respect to the ratio of the area of measuring the visual field as the total amount of the aperture area of each pore.In addition; Calculate the diameter of equivalent circle (having and the aperture area of pore diameter of a circle of the same area) of the pore of next door surface opening; With the accumulation area of the pore of next door surface upper shed (value after aperture area that will the pore below the specific diameter of equivalent circle is accumulated) with respect to the curve map (with reference to Fig. 3) after the linearize of diameter of equivalent circle march in, the diameter of equivalent circle that will become the pore of 50% the accumulation area that is equivalent to whole pore areas is directly calculated as the intermediate value opening.The diameter of equivalent circle of the pore of next door surface upper shed be 10 μ m above and less than the pore density of 40 μ m as in the pore of the per unit area upper shed on surface, next door, diameter of equivalent circle is to calculate more than the 10 μ m and less than the quantity of the pore of 40 μ m.
The porosity, intermediate value fine pore, 5 μ m are above and carry out through mercury penetration method less than the pore volume of 20 μ m, pore volume and the mensuration of pore distribution bias more than the 20 μ m.(10mm * 10mm * 10mm) be accommodated in the determination unit of system Autopore (the オ one ト Port ア) III of Micromeritics society in the unit after the decompression, imports mercury and pressurizes the test film that will cut out from ceramic honeycomb filter.Pressure during according to pressurization is obtained fine pore and the relation of accumulating pore volume with the relation that is present in the volume of bulged-in mercury in the pore in the test film.The pressure that imports mercury is 0.5psi (0.35 * 10 -3Kg/mm 2), the constant when calculating fine pore according to pressure is contact angle=130 °, surface tension is 484dyne/cm.The porosity according to the measured value of whole pore volume with the true specific gravity of cordierite as 2.52g/cm 3And try to achieve through calculating.
Thermal coefficient of expansion between 20～800 ℃ (CTE) uses other test films of cutting out from amplifier case and determined.
The darcy infiltration coefficient is to use Perm Automated Porometer (registration mark) 6.0 editions (Port one ラ ス マ テ リ ア Le ズ society) to make air mass flow be increased to 400cc/sec and the maximum of the venting quality measured from 30cc/sec.
To in the ceramic honeycomb filter of embodiment 1～26 and comparative example 1～9 remaining one carried out coal ash that the initial stage pressure loss, 2g/ rise be captured when collecting the pressure loss and catch the evaluation of collection efficiency.The result is as shown in table 7.
The initial stage pressure loss by with air with flow 10Nm 3The differential pressure of inflow side and outflow side (pressure loss) was represented when/min sent into the ceramic honeycomb filter that is fixed on the pressure loss testboard.With the pressure loss surpass 0.7 and be situation below the 1.0kPa as " zero ", the situation below the 0.7kPa as " ◎ ", will be estimated the initial stage pressure loss above the situation conduct " * " of 1.0kPa thus.
The pressure loss when coal ash that 2g/ rises is captured collection is 10Nm by to the ceramic honeycomb filter that is fixed on the pressure loss testboard in air mass flow 3Drop into the carbon dust of particle diameter 0.042 μ m under the state of/min with the speed of 3g/h, the pressure reduction (pressure loss) of inflow side when the coal ash adhesion amount of per 1 liter of filter volume becomes 2g and outflow side is represented.With the pressure loss surpass 1.2 but be situation below the 1.5kPa as " zero ", the situation below the 1.2kPa as " ◎ ", will be estimated the coal ash seizure collection pressure loss above the situation conduct " * " of 1.5kPa thus.
Catching collection efficiency and above-mentioned and obtain equally as follows, that is, to the ceramic honeycomb filter that is fixed on the pressure loss testboard, is 10Nm in air mass flow 3Speed input particle diameter with 3g/h under the state of/min is the carbon dust of 0.042 μ m; And utilize SMPS (Scanning Mobility Particle Sizer) (TIS society system 3936 models) instrumentation per minute to flow into population and the population of the carbon dust that flows out from amplifier case of the carbon dust of amplifier case simultaneously, according to from dropping into the population N that beginning flowed into the carbon dust of amplifier case in 3 minutes to 4 minutes InReach from the population N of the carbon dust of amplifier case outflow Out, utilize numerical expression: (N In-N Out)/N InObtain the seizure collection efficiency.With catch collection efficiency be 95% or more and less than 98% situation as " zero ", catching collection efficiency is the situation conduct " ◎ " more than 98%, and the seizure collection efficiency is estimated as " * " less than 95% situation.
Table 1
Figure BDA0000138074920000231
Table 1 (continuing)
Figure BDA0000138074920000232
Table 2
Figure BDA0000138074920000233
Table 3
Figure BDA0000138074920000241
Table 3 (continuing)
Figure BDA0000138074920000242
Table 4
Figure BDA0000138074920000243
Table 5
Figure BDA0000138074920000251
Table 5 (continuing)
Figure BDA0000138074920000252
Table 6
Figure BDA0000138074920000261
Table 6 (continuing)
Figure BDA0000138074920000271
Table 6 (continuing)
Figure BDA0000138074920000281
Table 7
Figure BDA0000138074920000291
Table 7 (continuing)
Table 7 (continuing)
Table 7 (continuing)
Figure BDA0000138074920000321
Table 7 (continuing)
Figure BDA0000138074920000331
Can know that according to table 7 ceramic honeycomb filter of embodiments of the invention 1～26 can be kept the lower pressure loss, and can improve the PM at the seizure collection beginning initial stage after the regeneration and catch collection rate.Wherein, Contain 50% respectively for using; Ceramic honeycomb filter among the embodiment 17,25 and 26 of the porous matter pore-creating made of 10% and 0% moisture; Though the seizure after can keeping the lower pressure loss and making regeneration is collected the PM seizure collection rate at beginning initial stage and is improved, and applies higher pressure during owing to extrusion molding, so the formed body after the extruding deforms even distortion has also taken place mould.Especially, to contain moisture be among the embodiment 26 that makes of 0% porous matter pore-creating material having used, because the mould moderate finite deformation, thereby can't carry out later extrusion molding.
Can know that on the other hand big for the intermediate value opening footpath of the pore of the next door of comparative example 1 and 4 surface upper shed, more than the 10 μ m and less than for the low density ceramic honeycomb filter of the pore of 40 μ m, it is low to catch collection efficiency.Can know in addition; For the little ceramic honeycomb filter in the aperture area rate of the pore of the next door of comparative example 2 and 5 surface upper shed and intermediate value opening footpath; The crushing that the initial stage pressure loss and coal ash 2g/L catch when collecting is all big; For the ceramic honeycomb filter of comparative example 5, because 10 μ m are above and lower less than the pore density of 40 μ m, so the seizure collection efficiency is low slightly for the ceramic honeycomb filter of comparative example 2.Can know that in addition the seizure collection efficiency of the ceramic honeycomb filter that the intermediate value opening footpath of the pore of the next door surface upper shed of comparative example 3 is big is low.And can know; For the aperture area rate of the pore of the next door of comparative example 6 surface upper shed and more than the 10 μ m and low less than the pore density of 40 μ m; 10 μ m are above and less than the big ceramic honeycomb filter of mean value of the circularity of the pore of 40 μ m; The crushing that coal ash 2g/L catches when collecting is big, and the seizure collection efficiency is low.Can know in addition, for the aperture area rate of the pore of the next door of comparative example 7 surface upper shed and more than the 10 μ m and less than for the low density ceramic honeycomb filter of the pore of 40 μ m, the crushing that the initial stage pressure loss and coal ash 2g/L catch when collecting is all big.And can know that the seizure collection efficiency that the porosity of comparative example 8 surpasses 60% ceramic honeycomb filter is low, thermal coefficient of expansion is big.Can know in addition; For more than the 10 μ m of comparative example 9 and low less than the pore density of 40 μ m, more than the 10 μ m and less than for the big ceramic honeycomb filter of the mean value of the circularity of the pore of 40 μ m; The crushing that coal ash 2g/L catches when collecting is big slightly, and the seizure collection efficiency is low.

Claims (11)

1. ceramic honeycomb structure, it has a plurality of streams of being separated by the next door of porous matter, it is characterized in that,
The porosity in said next door is 40～60%,
Aperture area rate at the pore of the surperficial upper shed in said next door is more than 15%, and said aperture area rate is meant total aperture area of pore of the per unit area upper shed on surface, next door,
Under the situation about representing by diameter of equivalent circle in the opening footpath of the pore of the surperficial upper shed in said next door; Intermediate value opening under the area benchmark of the pore of said opening directly is more than the 10 μ m and less than 40 μ m; Said diameter of equivalent circle is meant the diameter of a circle that has with the equal area of the aperture area of pore
Said diameter of equivalent circle is that 10 μ m are above and be 350/mm less than the density of the pore of 40 μ m 2More than,
Said diameter of equivalent circle is that 10 μ m are above and be 1～2 less than the mean value of the circularity of the pore of 40 μ m.
2. ceramic honeycomb structure according to claim 1 is characterized in that,
The darcy infiltration coefficient in said next door is 0.1 * 10 -12～2 * 10 -12m 2
3. ceramic honeycomb structure according to claim 1 and 2 is characterized in that,
Intermediate value fine pore when measuring the fine pore in said next door through mercury penetration method is more than the 5 μ m and less than 20 μ m,
Fine pore is below 10% of whole pore volume less than the pore volume of 2 μ m,
Fine pore is that the above pore volume of 40 μ m is below 10% of whole pore volume,
Pore distribution bias σ is below 0.5; Wherein, σ=log (D20)-log (D80), in the curve of relation of expression fine pore and accumulation pore volume, D20 representes to be equivalent to the fine pore under 20% the pore volume of whole pore volume; The same expression of D80 is equivalent to the fine pore under 80% the pore volume of whole pore volume; And D80＜D20, said accumulation pore volume is meant that the unit of said fine pore is μ m with the value after accumulating to the pore volume in specific porous footpath from the fine pore of maximum.
4. according to any described ceramic honeycomb structure in the claim 1 to 3, it is characterized in that,
The waste gas inflow side of said stream or waste gas outflow side are alternately sealed and are used as filter.
5. according to any described ceramic honeycomb structure in the claim 1 to 4, it is characterized in that,
Average next door thickness is 9.0～12mil, and average bee-hole density is 150～300cpsi.
6. according to any described ceramic honeycomb structure in the claim 1 to 5, it is characterized in that,
Thermal coefficient of expansion between 20～800 ℃ of said ceramic honeycomb structure is 13 * 10 -7/ ℃ below.
7. the manufacturing approach of a ceramic honeycomb structure will contain the base soil extrusion molding of cordierite raw material and pore-creating material and make cellular ceramic structural body, it is characterized in that,
Said cordierite raw material contains the silica of 15～25 quality %,
The average grain diameter of said silica is 20～30 μ m, and particle diameter is that the particle below the 10 μ m is below the 5 quality %, and particle diameter is that the above particle of 100 μ m is below the 5 quality %, and size distribution deviation SD is below 0.5, and sphericity is more than 0.5,
The amount of said pore-creating material is 5～40 quality % with respect to the cordierite raw material,
The average grain diameter of said pore-creating material is 15～50 μ m, and particle diameter is that the particle below the 5 μ m is below the 10 quality %, and particle diameter is that the above particle of 80 μ m is below the 5 quality %, and size distribution deviation SD is below 0.5, and sphericity is more than 0.5,
Wherein, SD=log (d80)-log (d20), in the curve of the relation of expression particle diameter and cumulative volume, d20 representes to be equivalent to the particle diameter under 20% the cumulative volume of whole volumes; The same expression of d80 is equivalent to the particle diameter under 80% the cumulative volume of whole volumes; And d20＜d80, said cumulative volume are meant that the unit of said particle diameter is μ m with the value after the accumulation of the particle volume below the specific particle diameter.
8. the manufacturing approach of ceramic honeycomb structure according to claim 7 is characterized in that,
Said pore-creating material is a porous matter polymer, and said pore-creating material particle has more than 30% and less than 50% space.
9. the manufacturing approach of ceramic honeycomb structure according to claim 8 is characterized in that,
The space of said pore-creating material particle contain moisture more than 80%.
10. according to the manufacturing approach of any described ceramic honeycomb structure in the claim 7 to 9, it is characterized in that,
The talcum that in said cordierite raw material, contains 40～43 quality %; The average grain diameter of said talcum is 1～10 μ m; In the curve of the relation of representing particle diameter and cumulative volume; The particle diameter d90 that is equivalent under 90% the cumulative volume of whole volumes is below the 30 μ m, and size distribution deviation SD is below 0.7, and said cumulative volume is meant the value after the accumulation of the particle volume below the specific particle diameter.
11. the manufacturing approach according to any described ceramic honeycomb structure in the claim 7 to 10 is characterized in that,
The shape factor of representing the dull and stereotyped degree of said talcum particle is more than 0.77.
CN201080037669.8A 2009-09-04 2010-09-02 Ceramic honeycomb structure and method for manufacturing same Active CN102481503B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2009205153 2009-09-04
JP2009-205153 2009-09-04
PCT/JP2010/065068 WO2011027837A1 (en) 2009-09-04 2010-09-02 Ceramic honeycomb structure and method for manufacturing same

Publications (2)

Publication Number Publication Date
CN102481503A true CN102481503A (en) 2012-05-30
CN102481503B CN102481503B (en) 2015-05-20

Family

ID=43649371

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201080037669.8A Active CN102481503B (en) 2009-09-04 2010-09-02 Ceramic honeycomb structure and method for manufacturing same

Country Status (6)

Country Link
US (2) US9074504B2 (en)
EP (1) EP2455153B1 (en)
JP (2) JP5630437B2 (en)
KR (2) KR101770654B1 (en)
CN (1) CN102481503B (en)
WO (1) WO2011027837A1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105392759A (en) * 2013-09-24 2016-03-09 日立金属株式会社 Ceramic honeycomb structure and production method therefor
CN105555738A (en) * 2013-09-24 2016-05-04 日立金属株式会社 Cordierite ceramic honeycomb structure and production method therefor
CN105999908A (en) * 2015-03-30 2016-10-12 日本碍子株式会社 Honeycomb structural body and method for manufacturing same
CN107159316A (en) * 2016-03-07 2017-09-15 日本碍子株式会社 Honeycomb structured body
CN107228000A (en) * 2016-03-25 2017-10-03 日本碍子株式会社 Honeycomb structured body
CN109160824A (en) * 2018-08-21 2019-01-08 武汉绿帆世纪科技有限公司 A kind of ceramic porous material and preparation method thereof based on MOFs
CN111744288A (en) * 2019-03-27 2020-10-09 日本碍子株式会社 Honeycomb structure and method for manufacturing honeycomb structure
CN111801151A (en) * 2018-11-07 2020-10-20 川崎重工业株式会社 Acid gas absorbing material and method for producing same
CN113557352A (en) * 2019-07-29 2021-10-26 株式会社电装 Exhaust gas purifying filter
CN115138397A (en) * 2021-03-30 2022-10-04 日本碍子株式会社 Honeycomb structure

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8821609B2 (en) 2010-04-01 2014-09-02 Hitachi Metals, Ltd. Ceramic honeycomb filter and its production method
JP5643692B2 (en) * 2011-03-25 2014-12-17 日本碍子株式会社 Honeycomb filter and manufacturing method thereof
US20140357474A1 (en) * 2013-05-30 2014-12-04 Corning Incorporated Formed ceramic substrate composition for catalyst integration
JP5667663B2 (en) * 2013-06-24 2015-02-12 日本碍子株式会社 Honeycomb structure
US10029939B2 (en) * 2015-02-27 2018-07-24 Corning Incorporated Ceramic composite beads and methods for making same
KR102465748B1 (en) 2015-03-24 2022-11-09 히타치 긴조쿠 가부시키가이샤 Ceramic Honeycomb Structure
EP3275853B1 (en) 2015-03-24 2020-04-22 Hitachi Metals, Ltd. Ceramic honeycomb structure
KR102439667B1 (en) 2015-03-24 2022-09-01 히타치 긴조쿠 가부시키가이샤 Ceramic honeycomb structure and manufacturing method thereof
JP6664248B2 (en) * 2016-03-25 2020-03-13 日本碍子株式会社 Honeycomb structure
JP6788515B2 (en) * 2017-02-02 2020-11-25 日本碍子株式会社 Sealed honeycomb structure
JP6802096B2 (en) * 2017-03-14 2020-12-16 日本碍子株式会社 Sealed honeycomb structure
WO2020214462A1 (en) * 2019-04-18 2020-10-22 Corning Incorporated Low bulk density, high geometric surface area honeycomb bodies
JP7229192B2 (en) * 2020-03-02 2023-02-27 日本碍子株式会社 honeycomb filter
JP7227177B2 (en) 2020-03-02 2023-02-21 日本碍子株式会社 honeycomb filter
JP7353217B2 (en) 2020-03-02 2023-09-29 日本碍子株式会社 honeycomb filter
JP7449720B2 (en) 2020-03-02 2024-03-14 日本碍子株式会社 honeycomb filter
JP7353218B2 (en) 2020-03-02 2023-09-29 日本碍子株式会社 honeycomb filter
JP7449721B2 (en) 2020-03-02 2024-03-14 日本碍子株式会社 honeycomb filter
JP7227178B2 (en) * 2020-03-02 2023-02-21 日本碍子株式会社 honeycomb filter

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1674972A (en) * 2002-06-26 2005-09-28 康宁股份有限公司 Magnesium aluminum silicate structures for DPF applications
CN1900493A (en) * 2001-09-13 2007-01-24 日立金属株式会社 Ceramic honeycomb filter

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61129015A (en) 1984-11-24 1986-06-17 Nippon Denso Co Ltd Filter for purifying exhaust gas and its preparation
JP2578176B2 (en) * 1988-08-12 1997-02-05 日本碍子株式会社 Porous ceramic honeycomb filter and method for producing the same
US5141686A (en) 1988-11-21 1992-08-25 Corning Incorporated Method for producing cordierite articles
JP2726616B2 (en) * 1993-12-15 1998-03-11 日本碍子株式会社 Porous ceramic honeycomb filter
EP0761279B1 (en) * 1995-08-22 2002-11-20 Denki Kagaku Kogyo Kabushiki Kaisha Honeycomb structure
JP2003040687A (en) 2000-06-30 2003-02-13 Ngk Insulators Ltd Honeycomb structured ceramic compact and its manufacturing method
JP3329798B2 (en) * 2000-10-06 2002-09-30 日立金属株式会社 Cordierite ceramic honeycomb structure
JP4094830B2 (en) 2000-11-24 2008-06-04 日本碍子株式会社 Porous honeycomb filter and manufacturing method thereof
JP4394329B2 (en) * 2001-03-01 2010-01-06 日本碍子株式会社 Manufacturing method of ceramic structure
CN1284802C (en) 2001-03-14 2006-11-15 积水化学工业株式会社 Hollow polymer particles, method for preparing hollow polymer particles, porous ceramic filter, and method for preparing porous ceramic filter
JP4715032B2 (en) 2001-05-25 2011-07-06 トヨタ自動車株式会社 Diesel exhaust gas purification filter
JP3727550B2 (en) 2001-05-30 2005-12-14 株式会社デンソー Exhaust gas purification filter and manufacturing method thereof
US6827754B2 (en) 2001-09-13 2004-12-07 Hitachi Metals, Ltd. Ceramic honeycomb filter
ATE372449T1 (en) * 2001-12-03 2007-09-15 Hitachi Metals Ltd CERAMIC HONEYCOMB FILTER
JP4227347B2 (en) * 2002-03-29 2009-02-18 日本碍子株式会社 Porous material and method for producing the same
CA2522916C (en) 2003-04-24 2011-11-22 Dow Global Technologies Inc. Improved porous mullite bodies and methods of forming them
JP4577752B2 (en) 2003-06-06 2010-11-10 日立金属株式会社 Ceramic honeycomb filter
JP2005103469A (en) * 2003-09-30 2005-04-21 Sekisui Chem Co Ltd Method of manufacturing heat-expansible microcapsule
DE112005000601T5 (en) * 2004-03-19 2007-03-01 Ngk Insulators, Ltd. Process for producing a porous ceramic structure
JP4361449B2 (en) * 2004-09-24 2009-11-11 日本碍子株式会社 Method for producing cordierite honeycomb structure
CN101137599B (en) 2005-03-10 2011-01-19 日本碍子株式会社 Honeycomb structure and method of manufacturing the same
JP2007045686A (en) 2005-08-12 2007-02-22 Ngk Insulators Ltd Method for manufacturing porous ceramic structure
US7485594B2 (en) 2005-10-03 2009-02-03 Dow Global Technologies, Inc. Porous mullite bodies and methods of forming them
ATE540907T1 (en) * 2005-11-30 2012-01-15 Corning Inc POROUS CERAMIC HONEYCOMB FILTER WITH CONTROLLED PORE SIZE DISTRIBUTION
FR2893861B1 (en) * 2005-11-30 2008-01-04 Saint Gobain Ct Recherches FILTRATION STRUCTURE OF GAS BASED ON CONTROLLED WALL SURFACE POROSITY SIC GAS
EP1997788B1 (en) * 2006-03-17 2012-11-28 NGK Insulators, Ltd. Process for producing a cordierite-based honeycomb structure
JP4904515B2 (en) * 2007-06-15 2012-03-28 独立行政法人産業技術総合研究所 Ceramic porous body
CN101959571B (en) * 2007-10-12 2013-06-12 日立金属株式会社 Cordierite ceramic honeycomb filter and process for producing the same
US8691361B2 (en) * 2008-07-28 2014-04-08 Hitachi Metals, Ltd. Ceramic honeycomb structure and its production method
US8187353B2 (en) * 2009-01-21 2012-05-29 Corning Incorporated Filtration structures for improved particulate filter performance
WO2011102487A1 (en) * 2010-02-22 2011-08-25 日立金属株式会社 Ceramic honeycomb structure and process for producing same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1900493A (en) * 2001-09-13 2007-01-24 日立金属株式会社 Ceramic honeycomb filter
CN1674972A (en) * 2002-06-26 2005-09-28 康宁股份有限公司 Magnesium aluminum silicate structures for DPF applications

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105392759A (en) * 2013-09-24 2016-03-09 日立金属株式会社 Ceramic honeycomb structure and production method therefor
CN105555738A (en) * 2013-09-24 2016-05-04 日立金属株式会社 Cordierite ceramic honeycomb structure and production method therefor
CN105392759B (en) * 2013-09-24 2018-01-26 日立金属株式会社 Ceramic honeycomb structural body and its manufacture method
CN105555738B (en) * 2013-09-24 2018-03-09 日立金属株式会社 Cordierite ceramic honeycomb structure and its manufacture method
CN105999908A (en) * 2015-03-30 2016-10-12 日本碍子株式会社 Honeycomb structural body and method for manufacturing same
CN107159316A (en) * 2016-03-07 2017-09-15 日本碍子株式会社 Honeycomb structured body
CN107159316B (en) * 2016-03-07 2020-10-30 日本碍子株式会社 Honeycomb structure
CN107228000B (en) * 2016-03-25 2020-03-31 日本碍子株式会社 Honeycomb structure
CN107228000A (en) * 2016-03-25 2017-10-03 日本碍子株式会社 Honeycomb structured body
CN109160824A (en) * 2018-08-21 2019-01-08 武汉绿帆世纪科技有限公司 A kind of ceramic porous material and preparation method thereof based on MOFs
CN109160824B (en) * 2018-08-21 2021-02-02 武汉摩尔安科技有限公司 Ceramic porous material based on MOFs (metal-organic frameworks) and preparation method thereof
CN111801151A (en) * 2018-11-07 2020-10-20 川崎重工业株式会社 Acid gas absorbing material and method for producing same
CN111744288A (en) * 2019-03-27 2020-10-09 日本碍子株式会社 Honeycomb structure and method for manufacturing honeycomb structure
CN111744288B (en) * 2019-03-27 2022-02-15 日本碍子株式会社 Honeycomb structure and method for manufacturing honeycomb structure
CN113557352A (en) * 2019-07-29 2021-10-26 株式会社电装 Exhaust gas purifying filter
CN113557352B (en) * 2019-07-29 2023-10-31 株式会社电装 Exhaust gas purifying filter
CN115138397A (en) * 2021-03-30 2022-10-04 日本碍子株式会社 Honeycomb structure
CN115138397B (en) * 2021-03-30 2023-11-14 日本碍子株式会社 honeycomb structure

Also Published As

Publication number Publication date
KR101770654B1 (en) 2017-08-23
EP2455153A4 (en) 2015-09-30
US20150251124A1 (en) 2015-09-10
JP5835395B2 (en) 2015-12-24
JP2014166635A (en) 2014-09-11
KR101770660B1 (en) 2017-08-23
WO2011027837A1 (en) 2011-03-10
KR20170008894A (en) 2017-01-24
US20120148792A1 (en) 2012-06-14
US9724633B2 (en) 2017-08-08
JPWO2011027837A1 (en) 2013-02-04
EP2455153B1 (en) 2018-10-31
JP5630437B2 (en) 2014-11-26
KR20120090054A (en) 2012-08-16
US9074504B2 (en) 2015-07-07
CN102481503B (en) 2015-05-20
EP2455153A1 (en) 2012-05-23

Similar Documents

Publication Publication Date Title
CN102481503B (en) Ceramic honeycomb structure and method for manufacturing same
CN102089058B (en) Ceramic honeycomb structure and process for producing same
CN102834158B (en) Ceramic honeycomb filter and method for producing same
JP5402638B2 (en) Cordierite ceramic honeycomb filter and manufacturing method thereof
JP5725247B2 (en) Method for manufacturing ceramic honeycomb structure
CN105008050B (en) Ceramic honeycomb structural body and its manufacture method
CN102365119B (en) Ceramic honeycomb structure and process for producing same
CN105392759A (en) Ceramic honeycomb structure and production method therefor
CN105555738A (en) Cordierite ceramic honeycomb structure and production method therefor
CN107250084A (en) Ceramic honeycomb structural body
CN107250083A (en) Ceramic honeycomb structural body and its manufacture method
CN1845885A (en) Ceramic honeycomb structure and ceramic body used for extrusion-molding the structure

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant